# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Guido Pampaloni' _publ_contact_author_email PAMPA@DCCI.UNIPI.IT _publ_section_title ; The Reactivity of 1,1-Dialkoxyalkanes with Niobium and Tantalum Pentahalides. Formation of Coordination Compounds, C-H and C-C Bonds Activation and the X-Ray Structure of the Stable Carboxonium Species [Me2C=CHC(=OMe)Me][NbCl5(OMe)] ; loop_ _publ_author_name 'Guido Pampaloni' 'Fabio Marchetti' 'Stefano Zacchini' # Attachment 'Ta2Cl6_OMe_2.CIF' data_ppp-1 _database_code_depnum_ccdc_archive 'CCDC 725347' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C4 H12 Cl6 O4 Ta2' _chemical_formula_weight 698.74 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ta Ta -0.7052 6.5227 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.170(2) _cell_length_b 9.062(2) _cell_length_c 10.634(3) _cell_angle_alpha 75.852(3) _cell_angle_beta 89.165(3) _cell_angle_gamma 85.452(3) _cell_volume 761.1(3) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4589 _cell_measurement_theta_min 2.325 _cell_measurement_theta_max 28.317 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.049 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 632 _exptl_absorpt_coefficient_mu 15.413 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.1577 _exptl_absorpt_correction_T_max 0.2592 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8153 _diffrn_reflns_av_R_equivalents 0.0417 _diffrn_reflns_av_sigmaI/netI 0.0556 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.98 _diffrn_reflns_theta_max 27.50 _reflns_number_total 3374 _reflns_number_gt 2875 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0415P)^2^+49.0290P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3374 _refine_ls_number_parameters 149 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0581 _refine_ls_R_factor_gt 0.0519 _refine_ls_wR_factor_ref 0.1674 _refine_ls_wR_factor_gt 0.1640 _refine_ls_goodness_of_fit_ref 1.191 _refine_ls_restrained_S_all 1.190 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.567(2) 0.033(2) 0.2516(14) 0.025(4) Uani 1 1 d . . . H1A H 0.4804 0.0881 0.1915 0.038 Uiso 1 1 calc R . . H1B H 0.5965 -0.0666 0.2336 0.038 Uiso 1 1 calc R . . H1C H 0.6640 0.0924 0.2403 0.038 Uiso 1 1 calc R . . C2 C 0.423(3) 0.428(2) 0.1837(17) 0.030(4) Uani 1 1 d . . . H2A H 0.5201 0.4078 0.1338 0.045 Uiso 1 1 calc R . . H2B H 0.4158 0.5351 0.1889 0.045 Uiso 1 1 calc R . . H2C H 0.3242 0.4091 0.1407 0.045 Uiso 1 1 calc R . . C3 C 0.938(2) -0.008(2) 0.7602(15) 0.021(3) Uani 1 1 d . . . H3A H 0.9110 0.0963 0.7079 0.032 Uiso 1 1 calc R . . H3B H 0.8400 -0.0649 0.7706 0.032 Uiso 1 1 calc R . . H3C H 1.0239 -0.0586 0.7167 0.032 Uiso 1 1 calc R . . C4 C 0.976(3) 0.431(2) 0.6772(18) 0.035(4) Uani 1 1 d . . . H4A H 1.0949 0.4267 0.6635 0.053 Uiso 1 1 calc R . . H4B H 0.9362 0.5352 0.6808 0.053 Uiso 1 1 calc R . . H4C H 0.9216 0.4040 0.6055 0.053 Uiso 1 1 calc R . . Cl1 Cl 0.7470(5) 0.2203(5) 0.4636(4) 0.0228(8) Uani 1 1 d . . . Cl2 Cl 0.4339(6) 0.3415(5) 0.6180(4) 0.0260(8) Uani 1 1 d . . . Cl3 Cl 0.1778(5) 0.1643(5) 0.4818(4) 0.0210(8) Uani 1 1 d . . . Cl4 Cl 1.2338(5) 0.2303(5) 0.9646(4) 0.0222(8) Uani 1 1 d . . . Cl5 Cl 0.8891(5) 0.3465(5) 1.0969(4) 0.0239(8) Uani 1 1 d . . . Cl6 Cl 0.6722(5) 0.1522(5) 0.9487(4) 0.0210(8) Uani 1 1 d . . . O1 O 0.5077(14) 0.0116(13) 0.3866(9) 0.018(2) Uani 1 1 d . . . O2 O 0.4349(13) 0.3306(12) 0.3116(10) 0.016(2) Uani 1 1 d U . . O3 O 0.9976(14) -0.0014(13) 0.8878(10) 0.018(2) Uani 1 1 d . . . O4 O 0.9399(13) 0.3282(12) 0.7952(11) 0.018(2) Uani 1 1 d . . . Ta1 Ta 0.46173(7) 0.19532(7) 0.46545(5) 0.01496(19) Uani 1 1 d . . . Ta2 Ta 0.95287(7) 0.19318(7) 0.95236(6) 0.01492(19) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.032(9) 0.035(10) 0.006(6) -0.004(6) 0.001(6) 0.005(8) C2 0.043(11) 0.019(9) 0.021(8) 0.005(7) -0.005(7) 0.005(8) C3 0.021(8) 0.027(9) 0.016(7) -0.007(6) -0.002(6) -0.002(7) C4 0.043(11) 0.034(11) 0.024(9) 0.006(8) 0.009(8) -0.005(9) Cl1 0.0185(17) 0.023(2) 0.0257(19) -0.0032(15) -0.0018(14) -0.0046(15) Cl2 0.037(2) 0.019(2) 0.0224(18) -0.0054(15) 0.0028(16) -0.0041(17) Cl3 0.0171(17) 0.022(2) 0.0241(18) -0.0060(15) -0.0009(14) 0.0011(14) Cl4 0.0188(18) 0.0184(19) 0.0288(19) -0.0042(15) 0.0009(14) -0.0037(14) Cl5 0.032(2) 0.0166(19) 0.0249(19) -0.0092(15) 0.0047(15) -0.0007(16) Cl6 0.0169(17) 0.023(2) 0.0199(17) -0.0007(15) -0.0015(13) 0.0009(14) O1 0.024(6) 0.018(6) 0.009(5) -0.003(4) 0.002(4) 0.009(4) O2 0.019(4) 0.009(4) 0.020(4) -0.003(3) -0.001(3) -0.003(3) O3 0.024(6) 0.019(6) 0.011(5) -0.008(4) -0.002(4) 0.004(4) O4 0.023(6) 0.005(5) 0.025(6) -0.001(4) 0.003(4) -0.001(4) Ta1 0.0168(3) 0.0136(3) 0.0133(3) -0.0015(2) -0.0018(2) 0.0004(2) Ta2 0.0161(3) 0.0136(3) 0.0137(3) -0.0013(2) -0.0009(2) 0.0007(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 O1 1.481(17) . ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C1 H1C 0.9800 . ? C2 O2 1.430(19) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? C3 O3 1.463(17) . ? C3 H3A 0.9800 . ? C3 H3B 0.9800 . ? C3 H3C 0.9800 . ? C4 O4 1.41(2) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? Cl1 Ta1 2.359(4) . ? Cl2 Ta1 2.331(4) . ? Cl3 Ta1 2.358(4) . ? Cl4 Ta2 2.356(4) . ? Cl5 Ta2 2.339(4) . ? Cl6 Ta2 2.355(4) . ? O1 Ta1 2.047(11) . ? O1 Ta1 2.132(11) 2_656 ? O2 Ta1 1.793(11) . ? O3 Ta2 2.049(11) . ? O3 Ta2 2.130(11) 2_757 ? O4 Ta2 1.813(11) . ? Ta1 O1 2.132(11) 2_656 ? Ta2 O3 2.130(11) 2_757 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 C1 H1A 109.5 . . ? O1 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? O1 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? O2 C2 H2A 109.5 . . ? O2 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? O2 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? O3 C3 H3A 109.5 . . ? O3 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? O3 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? O4 C4 H4A 109.5 . . ? O4 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? O4 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C1 O1 Ta1 120.3(10) . . ? C1 O1 Ta1 125.5(9) . 2_656 ? Ta1 O1 Ta1 110.9(4) . 2_656 ? C2 O2 Ta1 174.6(11) . . ? C3 O3 Ta2 120.3(9) . . ? C3 O3 Ta2 125.4(10) . 2_757 ? Ta2 O3 Ta2 110.2(4) . 2_757 ? C4 O4 Ta2 164.6(12) . . ? O2 Ta1 O1 94.3(4) . . ? O2 Ta1 O1 163.2(4) . 2_656 ? O1 Ta1 O1 69.1(4) . 2_656 ? O2 Ta1 Cl2 104.8(4) . . ? O1 Ta1 Cl2 160.7(3) . . ? O1 Ta1 Cl2 91.9(3) 2_656 . ? O2 Ta1 Cl3 91.6(4) . . ? O1 Ta1 Cl3 92.8(3) . . ? O1 Ta1 Cl3 86.4(3) 2_656 . ? Cl2 Ta1 Cl3 89.09(15) . . ? O2 Ta1 Cl1 91.8(4) . . ? O1 Ta1 Cl1 88.3(3) . . ? O1 Ta1 Cl1 90.7(3) 2_656 . ? Cl2 Ta1 Cl1 88.78(15) . . ? Cl3 Ta1 Cl1 176.36(13) . . ? O4 Ta2 O3 97.6(5) . . ? O4 Ta2 O3 166.2(4) . 2_757 ? O3 Ta2 O3 69.8(4) . 2_757 ? O4 Ta2 Cl5 103.3(4) . . ? O3 Ta2 Cl5 158.7(3) . . ? O3 Ta2 Cl5 89.7(3) 2_757 . ? O4 Ta2 Cl6 92.3(4) . . ? O3 Ta2 Cl6 87.0(3) . . ? O3 Ta2 Cl6 92.7(3) 2_757 . ? Cl5 Ta2 Cl6 88.14(14) . . ? O4 Ta2 Cl4 89.8(4) . . ? O3 Ta2 Cl4 93.4(3) . . ? O3 Ta2 Cl4 85.4(3) 2_757 . ? Cl5 Ta2 Cl4 90.71(15) . . ? Cl6 Ta2 Cl4 177.83(13) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C2 O2 Ta1 O1 -24(12) . . . . ? C2 O2 Ta1 O1 -34(12) . . . 2_656 ? C2 O2 Ta1 Cl2 154(12) . . . . ? C2 O2 Ta1 Cl3 -117(12) . . . . ? C2 O2 Ta1 Cl1 65(12) . . . . ? C1 O1 Ta1 O2 22.4(11) . . . . ? Ta1 O1 Ta1 O2 -176.9(5) 2_656 . . . ? C1 O1 Ta1 O1 -160.7(14) . . . 2_656 ? Ta1 O1 Ta1 O1 0.0 2_656 . . 2_656 ? C1 O1 Ta1 Cl2 -150.6(10) . . . . ? Ta1 O1 Ta1 Cl2 10.1(14) 2_656 . . . ? C1 O1 Ta1 Cl3 114.3(10) . . . . ? Ta1 O1 Ta1 Cl3 -85.0(5) 2_656 . . . ? C1 O1 Ta1 Cl1 -69.2(10) . . . . ? Ta1 O1 Ta1 Cl1 91.5(5) 2_656 . . . ? C4 O4 Ta2 O3 -86(5) . . . . ? C4 O4 Ta2 O3 -62(5) . . . 2_757 ? C4 O4 Ta2 Cl5 98(5) . . . . ? C4 O4 Ta2 Cl6 -174(5) . . . . ? C4 O4 Ta2 Cl4 7(5) . . . . ? C3 O3 Ta2 O4 -27.6(11) . . . . ? Ta2 O3 Ta2 O4 174.1(5) 2_757 . . . ? C3 O3 Ta2 O3 158.3(14) . . . 2_757 ? Ta2 O3 Ta2 O3 0.0 2_757 . . 2_757 ? C3 O3 Ta2 Cl5 141.3(9) . . . . ? Ta2 O3 Ta2 Cl5 -17.0(13) 2_757 . . . ? C3 O3 Ta2 Cl6 64.3(10) . . . . ? Ta2 O3 Ta2 Cl6 -94.0(5) 2_757 . . . ? C3 O3 Ta2 Cl4 -117.9(10) . . . . ? Ta2 O3 Ta2 Cl4 83.8(5) 2_757 . . . ? _diffrn_measured_fraction_theta_max 0.963 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.963 _refine_diff_density_max 4.121 _refine_diff_density_min -2.710 _refine_diff_density_rms 0.480 # Attachment 'Ta2Br6_OMe_2.CIF' data_pp-1 _database_code_depnum_ccdc_archive 'CCDC 725348' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C4 H12 Br6 O4 Ta2' _chemical_formula_weight 965.50 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ta Ta -0.7052 6.5227 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.510(4) _cell_length_b 7.174(4) _cell_length_c 9.206(5) _cell_angle_alpha 75.974(7) _cell_angle_beta 80.170(8) _cell_angle_gamma 76.556(8) _cell_volume 402.7(4) _cell_formula_units_Z 1 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2205 _cell_measurement_theta_min 2.297 _cell_measurement_theta_max 27.778 _exptl_crystal_description plate _exptl_crystal_colour pale-yellow _exptl_crystal_size_max 0.11 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.981 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 424 _exptl_absorpt_coefficient_mu 28.453 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.1089 _exptl_absorpt_correction_T_max 0.1631 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3442 _diffrn_reflns_av_R_equivalents 0.0493 _diffrn_reflns_av_sigmaI/netI 0.0594 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.30 _diffrn_reflns_theta_max 25.02 _reflns_number_total 1409 _reflns_number_gt 1114 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1047P)^2^+38.0200P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1409 _refine_ls_number_parameters 75 _refine_ls_number_restraints 19 _refine_ls_R_factor_all 0.0940 _refine_ls_R_factor_gt 0.0746 _refine_ls_wR_factor_ref 0.2086 _refine_ls_wR_factor_gt 0.1949 _refine_ls_goodness_of_fit_ref 1.106 _refine_ls_restrained_S_all 1.111 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group M1 Ta 0.48585(16) 0.93386(14) 0.19302(11) 0.0177(4) Uani 1 1 d U . . Br1 Br 0.2459(5) 1.2448(5) 0.2213(4) 0.0395(8) Uani 1 1 d U . . Br2 Br 0.7313(6) 0.9937(6) 0.3428(4) 0.0481(9) Uani 1 1 d U . . Br3 Br 0.7379(5) 0.6227(5) 0.1702(4) 0.0410(8) Uani 1 1 d U . . O1 O 0.354(3) 0.919(3) 0.011(2) 0.025(3) Uani 1 1 d U . . C1 C 0.222(5) 0.781(5) 0.026(3) 0.037(7) Uani 1 1 d U . . H1A H 0.3116 0.6521 0.0201 0.056 Uiso 1 1 calc R . . H1B H 0.1311 0.8236 -0.0546 0.056 Uiso 1 1 calc R . . H1C H 0.1339 0.7723 0.1243 0.056 Uiso 1 1 calc R . . O2 O 0.321(3) 0.795(3) 0.330(2) 0.032(3) Uani 1 1 d U . . C2 C 0.226(5) 0.647(4) 0.429(3) 0.033(7) Uani 1 1 d U . . H2A H 0.0876 0.6510 0.3990 0.049 Uiso 1 1 calc R . . H2B H 0.2055 0.6694 0.5322 0.049 Uiso 1 1 calc R . . H2C H 0.3179 0.5188 0.4259 0.049 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 M1 0.0197(6) 0.0223(6) 0.0114(6) -0.0028(4) 0.0069(4) -0.0124(4) Br1 0.0435(18) 0.0357(15) 0.0339(17) -0.0111(13) 0.0100(13) -0.0042(13) Br2 0.0473(19) 0.068(2) 0.0350(18) -0.0152(16) 0.0026(14) -0.0243(17) Br3 0.0412(18) 0.0373(16) 0.0384(18) -0.0047(13) 0.0022(14) -0.0042(13) O1 0.034(8) 0.025(7) 0.016(6) -0.001(5) 0.006(5) -0.017(5) C1 0.042(18) 0.050(18) 0.026(15) 0.003(13) -0.004(12) -0.036(14) O2 0.034(7) 0.039(5) 0.017(6) 0.009(7) 0.009(6) -0.017(5) C2 0.040(17) 0.024(13) 0.029(16) 0.005(10) 0.008(12) -0.019(11) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ta1 O2 1.775(17) . ? Ta1 O1 2.041(19) . ? Ta1 O1 2.149(17) 2_675 ? Ta1 Br2 2.449(4) . ? Ta1 Br1 2.451(3) . ? Ta1 Br3 2.475(3) . ? O1 C1 1.42(3) . ? O1 Ta1 2.149(17) 2_675 ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C1 H1C 0.9800 . ? O2 C2 1.41(3) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Ta1 O1 95.8(8) . . ? O2 Ta1 O1 165.7(8) . 2_675 ? O1 Ta1 O1 70.0(8) . 2_675 ? O2 Ta1 Br2 103.1(7) . . ? O1 Ta1 Br2 160.7(5) . . ? O1 Ta1 Br2 91.0(5) 2_675 . ? O2 Ta1 Br1 92.4(7) . . ? O1 Ta1 Br1 92.9(5) . . ? O1 Ta1 Br1 90.0(5) 2_675 . ? Br2 Ta1 Br1 90.29(13) . . ? O2 Ta1 Br3 88.2(7) . . ? O1 Ta1 Br3 89.3(5) . . ? O1 Ta1 Br3 90.0(5) 2_675 . ? Br2 Ta1 Br3 87.45(13) . . ? Br1 Ta1 Br3 177.74(13) . . ? C1 O1 Ta1 120.0(16) . . ? C1 O1 Ta1 127.7(17) . 2_675 ? Ta1 O1 Ta1 110.0(8) . 2_675 ? O1 C1 H1A 109.5 . . ? O1 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? O1 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? C2 O2 Ta1 167(2) . . ? O2 C2 H2A 109.5 . . ? O2 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? O2 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 Ta1 O1 C1 -14(2) . . . . ? O1 Ta1 O1 C1 164(3) 2_675 . . . ? Br2 Ta1 O1 C1 153.8(18) . . . . ? Br1 Ta1 O1 C1 -107(2) . . . . ? Br3 Ta1 O1 C1 74(2) . . . . ? O2 Ta1 O1 Ta1 -178.3(9) . . . 2_675 ? O1 Ta1 O1 Ta1 0.0 2_675 . . 2_675 ? Br2 Ta1 O1 Ta1 -10(2) . . . 2_675 ? Br1 Ta1 O1 Ta1 89.0(7) . . . 2_675 ? Br3 Ta1 O1 Ta1 -90.2(7) . . . 2_675 ? O1 Ta1 O2 C2 83(9) . . . . ? O1 Ta1 O2 C2 77(10) 2_675 . . . ? Br2 Ta1 O2 C2 -93(9) . . . . ? Br1 Ta1 O2 C2 176(9) . . . . ? Br3 Ta1 O2 C2 -6(9) . . . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 25.02 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 6.828 _refine_diff_density_min -3.193 _refine_diff_density_rms 0.657 # Attachment 'C8H16Cl5NbO2.CIF' data_p-1 _database_code_depnum_ccdc_archive 'CCDC 725349' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C8 H16 Cl5 Nb O2' _chemical_formula_weight 414.37 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Nb Nb -2.0727 0.6215 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.552(3) _cell_length_b 8.881(5) _cell_length_c 13.589(7) _cell_angle_alpha 85.974(6) _cell_angle_beta 89.238(6) _cell_angle_gamma 76.913(6) _cell_volume 768.2(7) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4139 _cell_measurement_theta_min 2.360 _cell_measurement_theta_max 28.2535 _exptl_crystal_description prism _exptl_crystal_colour pale-yellow _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.791 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 412 _exptl_absorpt_coefficient_mu 1.637 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.7571 _exptl_absorpt_correction_T_max 0.8278 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6875 _diffrn_reflns_av_R_equivalents 0.0545 _diffrn_reflns_av_sigmaI/netI 0.0602 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.50 _diffrn_reflns_theta_max 25.25 _reflns_number_total 2747 _reflns_number_gt 2370 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1196P)^2^+9.6820P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2747 _refine_ls_number_parameters 150 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0873 _refine_ls_R_factor_gt 0.0798 _refine_ls_wR_factor_ref 0.2269 _refine_ls_wR_factor_gt 0.2205 _refine_ls_goodness_of_fit_ref 1.084 _refine_ls_restrained_S_all 1.084 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Nb1 Nb 0.65210(12) 0.22165(9) 0.22584(6) 0.0221(3) Uani 1 1 d . . . Cl2 Cl 0.5145(3) 0.4280(2) 0.32642(16) 0.0263(5) Uani 1 1 d . . . Cl3 Cl 0.8109(3) 0.0167(3) 0.12218(17) 0.0272(5) Uani 1 1 d . . . Cl4 Cl 0.7076(3) 0.4121(2) 0.09854(16) 0.0251(5) Uani 1 1 d . . . Cl5 Cl 0.5931(3) 0.0453(3) 0.35282(17) 0.0272(5) Uani 1 1 d . . . Cl6 Cl 0.9948(3) 0.2110(3) 0.28099(18) 0.0321(6) Uani 1 1 d . . . O1 O 0.4074(9) 0.2253(7) 0.1577(5) 0.0251(13) Uani 1 1 d . . . C1 C 0.3020(14) 0.2220(10) 0.0688(6) 0.0242(18) Uani 1 1 d . . . H1A H 0.3095 0.3138 0.0257 0.036 Uiso 1 1 calc R . . H1B H 0.1550 0.2215 0.0827 0.036 Uiso 1 1 calc R . . H1C H 0.3680 0.1283 0.0361 0.036 Uiso 1 1 calc R . . C2 C -0.1855(16) 0.6791(12) 0.4825(8) 0.035(2) Uani 1 1 d . . . H2A H -0.2777 0.6248 0.4501 0.053 Uiso 1 1 calc R . . H2B H -0.2693 0.7747 0.5074 0.053 Uiso 1 1 calc R . . H2C H -0.1122 0.6124 0.5376 0.053 Uiso 1 1 calc R . . C3 C -0.0296(14) 0.7180(10) 0.4102(7) 0.0261(19) Uani 1 1 d . . . C4 C 0.1178(16) 0.8101(12) 0.4452(7) 0.031(2) Uani 1 1 d . . . H4A H 0.2626 0.7554 0.4334 0.047 Uiso 1 1 calc R . . H4B H 0.0972 0.8229 0.5159 0.047 Uiso 1 1 calc R . . H4C H 0.0898 0.9122 0.4091 0.047 Uiso 1 1 calc R . . C5 C -0.0253(14) 0.6663(10) 0.3177(7) 0.025(2) Uani 1 1 d . . . H5 H -0.1239 0.6065 0.3045 0.030 Uiso 1 1 calc R . . C6 C 0.1101(13) 0.6920(9) 0.2393(7) 0.0225(18) Uani 1 1 d . . . C7 C 0.1126(14) 0.6172(11) 0.1450(6) 0.0252(19) Uani 1 1 d . . . H7A H 0.0416 0.6936 0.0938 0.038 Uiso 1 1 calc R . . H7B H 0.0400 0.5321 0.1536 0.038 Uiso 1 1 calc R . . H7C H 0.2579 0.5763 0.1253 0.038 Uiso 1 1 calc R . . C8 C 0.3809(16) 0.8112(12) 0.1760(8) 0.034(2) Uani 1 1 d . . . H8A H 0.4776 0.7138 0.1616 0.051 Uiso 1 1 calc R . . H8B H 0.4606 0.8836 0.1983 0.051 Uiso 1 1 calc R . . H8C H 0.3020 0.8566 0.1162 0.051 Uiso 1 1 calc R . . O2 O 0.2359(10) 0.7810(7) 0.2531(4) 0.0236(13) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Nb1 0.0237(5) 0.0208(5) 0.0224(5) -0.0123(3) 0.0043(3) -0.0033(3) Cl2 0.0267(11) 0.0257(11) 0.0265(11) -0.0158(9) 0.0030(9) -0.0021(8) Cl3 0.0230(11) 0.0277(11) 0.0311(12) -0.0188(9) 0.0014(9) -0.0012(8) Cl4 0.0235(11) 0.0285(11) 0.0247(11) -0.0094(9) 0.0001(8) -0.0062(8) Cl5 0.0256(11) 0.0263(11) 0.0300(12) -0.0089(9) 0.0018(9) -0.0047(9) Cl6 0.0228(11) 0.0437(14) 0.0302(12) -0.0109(10) -0.0004(9) -0.0062(9) O1 0.021(3) 0.025(3) 0.029(3) -0.014(3) 0.000(3) -0.001(2) C1 0.024(4) 0.028(5) 0.022(4) -0.011(4) -0.007(4) -0.006(4) C2 0.030(5) 0.041(6) 0.032(5) -0.011(4) 0.011(4) -0.001(4) C3 0.025(5) 0.021(4) 0.031(5) -0.009(4) -0.001(4) 0.001(3) C4 0.039(5) 0.035(5) 0.023(5) -0.022(4) 0.005(4) -0.011(4) C5 0.021(4) 0.025(5) 0.034(5) -0.020(4) 0.001(4) -0.009(3) C6 0.021(4) 0.017(4) 0.028(5) -0.011(3) -0.006(4) 0.001(3) C7 0.024(4) 0.034(5) 0.020(4) -0.020(4) 0.002(4) -0.006(4) C8 0.032(5) 0.031(5) 0.043(6) -0.015(4) 0.013(4) -0.014(4) O2 0.028(3) 0.024(3) 0.021(3) -0.015(2) 0.001(3) -0.006(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Nb1 O1 1.855(6) . ? Nb1 Cl5 2.336(3) . ? Nb1 Cl6 2.356(3) . ? Nb1 Cl2 2.368(2) . ? Nb1 Cl4 2.416(2) . ? Nb1 Cl3 2.417(2) . ? O1 C1 1.404(10) . ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C1 H1C 0.9800 . ? C2 C3 1.488(13) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? C3 C5 1.366(13) . ? C3 C4 1.501(13) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 C6 1.416(13) . ? C5 H5 0.9500 . ? C6 O2 1.288(11) . ? C6 C7 1.482(11) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 O2 1.457(11) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Nb1 Cl5 95.2(2) . . ? O1 Nb1 Cl6 168.4(2) . . ? Cl5 Nb1 Cl6 92.71(9) . . ? O1 Nb1 Cl2 97.44(19) . . ? Cl5 Nb1 Cl2 89.58(9) . . ? Cl6 Nb1 Cl2 91.06(8) . . ? O1 Nb1 Cl4 85.1(2) . . ? Cl5 Nb1 Cl4 177.79(8) . . ? Cl6 Nb1 Cl4 87.34(9) . . ? Cl2 Nb1 Cl4 88.21(9) . . ? O1 Nb1 Cl3 85.14(19) . . ? Cl5 Nb1 Cl3 92.30(9) . . ? Cl6 Nb1 Cl3 86.11(8) . . ? Cl2 Nb1 Cl3 176.67(8) . . ? Cl4 Nb1 Cl3 89.91(9) . . ? C1 O1 Nb1 150.3(6) . . ? O1 C1 H1A 109.5 . . ? O1 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? O1 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? C3 C2 H2A 109.5 . . ? C3 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? C3 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? C5 C3 C2 119.0(8) . . ? C5 C3 C4 124.0(8) . . ? C2 C3 C4 117.0(8) . . ? C3 C4 H4A 109.5 . . ? C3 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C3 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C3 C5 C6 127.1(8) . . ? C3 C5 H5 116.5 . . ? C6 C5 H5 116.5 . . ? O2 C6 C5 117.7(7) . . ? O2 C6 C7 120.5(8) . . ? C5 C6 C7 121.9(8) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? O2 C8 H8A 109.5 . . ? O2 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? O2 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C6 O2 C8 120.6(7) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag Cl5 Nb1 O1 C1 -135.2(11) . . . . ? Cl6 Nb1 O1 C1 -2.5(19) . . . . ? Cl2 Nb1 O1 C1 134.5(11) . . . . ? Cl4 Nb1 O1 C1 47.0(11) . . . . ? Cl3 Nb1 O1 C1 -43.4(11) . . . . ? C2 C3 C5 C6 179.7(9) . . . . ? C4 C3 C5 C6 -1.7(15) . . . . ? C3 C5 C6 O2 -4.4(14) . . . . ? C3 C5 C6 C7 174.2(9) . . . . ? C5 C6 O2 C8 179.4(8) . . . . ? C7 C6 O2 C8 0.8(12) . . . . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 25.25 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 3.188 _refine_diff_density_min -2.382 _refine_diff_density_rms 0.230